Synthetic resin and composition containing it



Patented Dea?l1,l934' 1,984,153

UNITED STATES PATENT OFFICE! 1,984,153

sYN'lrns'nc aasnv annicomosrrron com-ammo n Gordon D; Patterson}Wilmington, and RoyAllen Shive, .Bellemoor, DeL, assignor tell. I. do.-Pont de Nemours & Company, Wilmington, Del,

. acorporaflon of'Delaware No Application October 26, 1929.

, Serial No. 402,790

6" (caste-s;

- This invention relates to. the of synthetic an-open kettle at 200 0.for about three hours resins and compositions containing them and. andallowedtocool to 170 C. The product, which more'particularlmtomethodsofimproving resinis a thin light brown resinous mass, is then ouscondensation products of polyhydric alcohols treated with 10% by weightof commercial lith-r and poLvbasic acids and compositions containingarge, based on the weight of the finished resin, 5

them. and stirred thoroughly, holding'the temperature Various methodshave been proposedior manuat 170? C. for fifteen minutes. The mixture isiacturing polyhydric alcohol-polybasic acid resins then thinned with 150partsby weight of solvent and compositionsjcontaining such resins, butprenaphtha and centrifuged to remove excess lithl0 vious products withwhich we are familiar, which arge and other undesirable compounds. weresufiicientiy flexible for most practical appli- E I IN 2 cations, hadeither insumcient water resistance, t V or weretoo slow drying, andtheir use was there- 38.64 parts by weight of phthalic anhydride, forerestricted in many fields for which their 27.54 parts by weightof linsedoil acids, 13.34 other desirable characteristics made them highlyparts by weight of China wood oil acids'and 20.48 desirable. v parts by'weight of glycerol are heated together We havediscovered that varioususeful propin an open kettle at 200 C; for four hours, at erties, suchas improved water resistance, inwhich stage the resinous materialwill beof a creased rate of set-up and increased hardness, liquid consistency.The finished material can be imparted to modified polyhydric a'1- isthen allowedto cool tofl'm C. and8% by 0- cohol-polybasic acid resins bytreating themv weight (based 'on the finishedresino'us product) a withsuitable agents, such as litharge. This of commercial iithar'ge is addedand Stirr Vigor may be carried out in various ways,- although il ly'frjflf e'n minutes-h ldin he mp rawe have herein indicated the twopreferred methtul'e at This mixture is -1 thinned 85 ods, which includethe cooking of the agent with w h 35'parts y W i h Of Solvent naptha andthe completed or substantially completed resin, n ifug d. or itsincorporation into a composition contain- Exam? No 3 ing the resin alongwith the pigment combination.

Bythe term modified polyhy r c alcohol-poly 6758 pa s bvtw sht or nawood oil. and basic acid resin, as used herein, we mean the 9.4! partsby weight of glycerol are heated to 30 resinous condensation productresulting from the set er. i a c os d v sel a i a c d t interaction ofone or more polyhydric alcohols, 225 C. until the mixture ishomogeneous, which one or more polybasic acids, and one or more ofusually requires about one hour. 22.59 parts the following ingredients,to-wit: drying oils, by weight of phthalic anhydrideare then added Isemi-drying oils, non-drying oils, and monobasic. and the heating isthen, continued, holding the organic acids, especially those derivedfrom drytemperature at 225 C. for'two-and 'a half hours, ing oils,semi-drying oils, and non-drying oils, at which stage the resinousmaterial will have a with or without other ingredients, such asnatmedium string (as judged bythe -usual varnish ural resins and othersynthetic resins. practice). The'material is then allowed to cool 49With the above and other objects inview. which t0 160 C; and 10% byweight'of commercial will be apparent as the description proceeds, welithargeibased on the weight of the finished resin) have set forth ourinvention in the following is added and the'mi rture stirred vigorouslyfor specification, and have included the following ezfifte n minutes,holding the temperature 160C.

amples by way of illustration and not as alimitamixture is th n inn h150 m by mm v weight or solvent naptha'and oenti-ii 1 Example No. 1zeampleilvo'. 4

46.31 parts by weight or phthalic n rdride, 37.97 parts by weight orphthalic'i so. I 30.96 parts by weight of linseed oil acids and 22.1330.80 parts by weight of linseedoll acids, 2.82 parts by weight ofglycerol are heated together in, parts by weight of China wood oil and18.4%

ture of coating compositions in the usual manner 'Substantialhr zincoxide tree lithopone by weight of glycerol are heated together in anopen kettle at-200 C, for sixhours, at which stage the resinous materialsistency. The temperatureis then allowed to drop to 170 C. and 7%byweight of commercial litharge (based on the weig t of the finishedresin) is added and the mixture stirred thoroughly for fifteen minutesat 170 C. The thoroughly stirred mixture is then thinned with 110 partsby weight of a solvent mixture containing equal parts byweight ofsolvent naptha and turpentine substitute and centrifuged.

The above resins may be used in the manufacand' as indicated in thefollowing examples:

Example No.5

Parts by weight Iron oxide"; 19.7 Lamp black 2.4 Asbestine 5.9 Chinaclay 7.5 Talc 5.9 13.0

Lithargeeated resin from Example 1 Solvent naptha 4--.

The pigments are mixed with suilicient oi the resin, dissolved insolvent naptha, to develop a consistency suitable for grinding in one ofthe standard devices for grinding and dispersing pigments. Following thenormal grinding period, the composition is thinned to applicationconsistency with the remainder of the resin solution and such-additionalnaptha as may be necessary.

Example No.

A black enamel is formed ment with enough of the resin to give a goodgrinding consistency and thinning with the remainder or the formula thatis, the rest or the resin,.the solvents and the drier).

' Example No. 7

. Parts by weight (i.,e.,"containing les's than 0.01 01' 1% or zincoxide) 34.98 Chinese blue l l 1.79 Resin solution of Example 4 50.00

. Cobalt linoleate (drier) 1.60 Hl-flash naptha 3.71 Turpentinesubstitute". 7.92

A'blue enarnel is prepared by mixing the above ingredients in the mannerindicated-tor Example By way of illustration,

will beof a thin liquid constan by grinding the pigor pigmenting theresin to form a pigmented nimiorming composition:

Ea:ample No. 8 y

' Parts by weight Iron .oxide 8.4 Carbon black 1.6 Asbestine 3.8 Chinaclay 4.8 -Ta1 as Litharge 1 0.7 Resin 7 14.1 Hi-flash naptha 18.8-Mineral spir 16.6 Toluol 27. 1

The resin used in this example was prepared by mixing the-followingingredients and heating for approximately two hours at 225 Parts by aweight Glycerol 20.37 Phthalic anhydrlde 37.34 Linseed oil acids 29.38China wood oil acids 12.91

The resin and litharge-in the above formula, together with suflicientnaptha to reduce resin viscosity and permit grinding, are intermixed andground in a suitable device, such as a ball mill, for several hours, oruntil a uniform state of fineness and distribution the pigments areadded, together with additional naptha to develop grinding consistency,and the compostion subjected to the period of grinding d for theproduct, say 12 hours, in a ball mill operation. The mill charge is thenreduced to suitable application consistency with naptha.

, Example No. 9

- Parts by weight Asbest 9.7

China clay 4.6

Lithopone 11.6

Carbon black 0.1

Barytes 17.1

Silica 8.6 'Litharge v 1.1 Res 10.6 High-flash naptha 31.7

Mineral spirits -4 4.9

The resin used in this example was prepared by mixing the followingingredients and heating for approximately 3 hours at 200 C.:

- Parts v by weight Glycerol." 22.73

Phthalic anhydrlde- 46.31 oil acids-.. 30.96

solution .(prepared with a portion ofthe naptha) the pigments added atonce and sufilcient additional naptha added to develop a consistency thefollowing examples show incorporation of agents during the processsuited to the grinding or dispersing device to be used. Following anormal dispersing cycle, the

has been attained. Then addition, v

. 4. Presence of all resin and all litharge in grind. However, in manycases, the desired improvement 'ean'be obtained by efliciently mixingthe litharge into the mill base, following the normal grinding period,or into' the finished product; compodtions so treated normally requirelarger quantitiesof litharge and are more likely to be subject tochanges in consistency on ageing.

Although the above examples are limited to the use of glycerol andphthalicanhydride, these maybe replaced in whole or in part by otherpolyhydric alcohols andother polybasic acids;

Similarly, the linseed oil acids, China wood oil acids and China woodoil used as the modifying ingredients, in the above examples, may bereplaced in whole or in part by other ingredients, such as perilla oil,fish oil, soya bean oil and other drying and'semi-drying oils ortheacids derived from these oils, as well as non-drying oils or theacids derived from non-drying oils, and various resins, such as rosin,i'longo, kauri and dammar.

Likewise, although the above examples are limited to the use of lithargeas the agentjoriimparting the desired water resistance and other specialproperties, we desire to have it understood that equivalent agents, suchas 'litharge containing substances, may be used.

It will also be apparent that although only two specific methods havebeen setfor'th above for the incorporation of the litharge, each ofthese methods may be modified in various ways. For example, the lithargemaybe added at :any time after partial esterification has taken'placeanby subsequently reheating the resin and incorporating the lithargetherewith. Similarly, the excess litharge, and other undesirablecompounds, may

'be removed by other means than centrifuging,

such as sedimentation .or filtration after solution.

- Likewise,'with resins of a liquid consistency,

we have-found it to be satisfactory to incorporate the litharge merelybyJagitation therewith, although heating may be resorted to if desired.

We also desireit understood that, where desired, treatment of the resinin the manner described herein may be. repeated several times to eilectthe improvement desired. Other methods within the scopeof the appendedclaims will readilysuggest themselves to those skilled in the art,

andsuch methods may be substituted for those set forth herein.

1 We desire to point out that the amount of litharge which is to be usedwill vary with the particular resin, with the pigment combination,

For most purposes wehave found that it is satis-. factory to start withfrom 1 to 10% ot litharge,

based on the resin, and this results in-the retention in the ultimatecomposition of fronra trace to 5% of soluble lead, based on the resin.

While some excess of litharge may generally be used in the method setforth in Examples 1-4 without disadvantageous results, and sometimeseven with advantage to acceleratethe reaction, it

= is desirable to remove or render this excess inactive to avoid slowprogress of the reaction in the finished product. Otherwise, suchcontinuing reactions might impair the latter by separation of insolublelead compounds or by causing liverlng, gelling, brittleness, or pooradhesion. When practicing the methodset forth in Examples 8-9,- however,it is not possible to remove the agent when it has once been added.Consequently, greater care must\be taken, when practicing this method,to avoid using an objectionable (EXCESS. 'r

Although we have stressed herein theimproved water resistance, theincreased rate of set up of the resulting composition, and the increasedhardness, which are imparted to modified polyhydric alcohol-polybasicacid resins by our invention, we desire to have it'understood-that thereare other important advantages. such as the elimination of after-tack.These advantages are especially important in the field of quickdrying.enamels, or 'undercoats for metals, such as automobiles, in which it isdesirable that the film set up quickly to a degree of hardness whichwill permit the carrying out of such operations as knife glaaing,sanding, or recoating within specified time limits at as low atemperature as possible, and preferably at room temperature.

From the above explanation and examples it will be apparent that we havedeveloped new and useful methods o; treating modified polyhydricalcohol-polybasic 'acid resins, which gives them 1 proved waterresistance, an increased rate of set up, and increased hardness, as wellas other desirable properties, and renders them highly use- I ful for avariety of commercial uses.

It will also be apparent that we have developed new-and useful coatingcompositions containing such resins, and' that these resins may also beincorporated in other types of, compositions, such as in varnishes,impregnating compositions and molding compounds.

While we do not desire to be restricted by any particular theoryunderlying our invention, we believe that in modified polyhydricalcohol-polybasic acid resins drying is retarded and water sensitivityis increased due to the presence of free glycerol or only partiallycombined glycerol. It

is well knownthat glycerol reacts with litharge to form a complexinsoluble substance. By taking advantage of this unique reaction oflitharge and litharge containing compounds with glycerol and thepartially reacted glycerol of the resin reaction, and treating suchresins with litharge, we have .found that the desired improvement iseffected, and we believe that it is due to the removal of those bodiesindicated herein as being responsible for the poordrying and watersensitivity characteristics. 4

As many apparently widely different embodiments of this invention may bemade without de parting from the spirit and scope thereof, it is to beunderstood that we do not limit ourselves to the specific embodimentsthereof except as de- Media the appended claims.

We claim;

. 1. A composition of matter comprising the.

resinous reaction product of glycerol, phthalic anhydride, and a memberof the group. which consists of drying oils and drying oil acids,litharge in the ratio of from substantially 14.0% of the weight of theresin, and pigment and solvent, said composition drying rapidly andbeing highly water resistant when laid down in thin films.

2. A process of producing resins having improved water resistanceandrapid drying, which comprises reacting glycerol, a vdrying oil andlitharge in an amount not exceeding 10% of the glycerol and drying oil,adding phthalic anhydride, and heating to resinification.

3. A composition of matter comprising in combined form the resinousreaction product of glycerol, 2. poiycarboxylic acid, and a member of.the group which consists of drying oils and drying oil acids, andlitharge in the ratio of from substantially 1-10% of the weight of theresin, said composition drying rapidly and being highly waterresistantwhen laid down in thin mm.

4. A process of producing resins having improved, water resistance andrapid drying which comprises reacting glycerol, a polycarboxylic acid,and at least one member 91 the group consisting of drying oils' anddrying oil acids, and adding litharge thereto in the ratio of 1-10% oitheweightv of the resin.

5. A rapidly drying, water resistant, resinous composition of mattercontaining in combined form litharge and the radicals of glycerol,phthalic anhydride, and drying oil acids, said composition having from atrace up to 5% of soluble lead.

- 6. .A process of improving the water resistance of resins formed fromglycerol, phthalic anhydride, and a member oi'the group consisting ofdrying oils and drying oil' acids which comprises heating the resiningredients at a temperature of 170-225" C. for 2 to 6 hours until aresin is produced, allowing the resin to cool but not solidify, addingslowly and with agitation 1 to 10% litharge based on the' weight of theresin, cutting the resin in a solvent, and removing freelitharge and anyinsoluble lead compounds from the resin solution. I GORDON D. PATTERSONROY ALLEN SHIVE;

